High temperature and high pressure aqueous solutions have an enormous number of applications in sciences and industries, including geosciences, synthesis and deposition of ceramics, supercritical water oxidation, fossil, nuclear, and geothermal power generation, pulp and paper production, and chemical productions. Potentiometric and pH measurements provide important information for studying thermodynamics and electrochemistry in high temperature aqueous solutions and in-situ monitoring and control of physical and chemical processes, e.g. speciation and corrosion, in industrial systems. More and more electrochemical sensors are used in industries. However, there are only a few devices having pH sensing electrodes for use during measurement in high temperature environments. Currently, the only primary and reliable pH sensing electrode available for use at high subcritical and supercritical temperatures ( greater than 374xc2x0 C.) is the Yttria-Stabilized Zirconia (YSZ) membrane electrode.
Two typical designs of YSZ electrodes used in the laboratory are shown in FIGS. 1 and 2. The electrode 10 of FIG. 1 is a YSZ tube 12 with a closed tip 14 and an open top 22. The closed tip 14 of the tube 12 is filled with a small amount of Hg|HgO paste 16. A Platinum (Pt) wire 18 that is partially covered with a shrinkable PTFE tube is placed in the tube 12, whereby the uncovered portion of the PT wire 18 is inserted into the Hg|HgO paste 16. The tube 12 is then filled with zirconia sand 20. The Pt wire 18 is used to provide electrical contact. The open top 22 of the tube 12 is typically sealed with epoxy 24 over the sand 20. The whole tube 12 is fitted into a CONAX fitting 26 at the top 22 of the tube 12 whereby the CONAX fitting 26 is a tube fitting used for gripping and sealing a tube. The wall of the tube 12 is the boundary separating the high pressure fluid (typically 300 bars) and the low pressure outside of the system. Under high pressures, the tube 12 will break, especially at the point where the CONAX fitting 26 grips t he YSZ tube 12. The electrode 27 of FIG. 2 is designed to eliminate breaking at the gripping location of the CONAX fitting 26. The electrode 27 utilizes complex techniques of joining ceramics to metals, such as brazing, to produce a tube 12 having an upper portion 28 of metal and a lower portion 30 of ceramic. Thus, allowing the CONAX fitting 26 to grip the metal upper portion 28 part of the tube 12. The problem with the metal-ceramic electrode 27 of FIG. 2 is that the metal-ceramic joint is normally not strong enough to sustain high temperatures and high pressures for a long period of time. Other methods of joining metals to ceramics have been tried or proposed. However, these methods are either not reliable or extremely costly.
The object of the present invention is to provide a more reliable YSZ membrane electrode.
The present invention is an improved yttria-stabilized zirconia electrode having a ceramic tube. The electrode is improved by replacing the method of sealing the electrode with an epoxy seal and filling the tube with a ceramic glue without completely filling the tube. The ceramic glue is added in a small amount and the ceramic glue is heated in the tube before the next small amount of ceramic glue is added, until the final amount of ceramic glue is added and heated. Also, an area of cover on a wire in an area between a top of the ceramic glue and a top of the tube is partially removed. A sealing glue above the top of the ceramic glue that adheres to the wire at the removed area of the cover, adheres to the tube and seals the top of the tube. Finally, an outside portion of the wire which extends beyond the top of the tube is gripped with a CONAX fitting, instead of the fitting gripping the tube.